Cyano- and thiocyanato-derivatives of the hexachlorophosphate ion (PCl6–)

Abstract

The preparation and identification in solution of several new cyano- and thiocyanato-derivatives of the hexachlorophosphate (PCl₆^–) ion are described. The cyano-complexes [PCl_6–n(CN)_n]^–(n= 1–3) and the hexathiocyanatophosphate ion P(NCS)₆^– have been isolated as tetra-n-alkylammonium salts and further characterised by elemental analysis, ³¹P n.m.r., and (in some cases) vibrational spectroscopy. The mer isomer of the [PCl₃(CN)₃]^–ion has been obtained pure and the fac isomer in a less pure state (ca. 3 : 1 fac: mer) by different preparative routes. lsomeric configurations in the chlorothiocyanatophosphate series [PCl_6–n(NCS)_n]^– have been assigned on the basis of the pairwise interaction method.